Chiral DMAP analogues offer unique reactivity and versatility as Lewis base catalysts in a wide array of reactions.1 There is a significant demand to evolve novel practical methodologies targeting direct mono-N-functionalization of C2-symmetrical diamines.Herein, we have anticipated that the chiral 2-aminoDMAP derived from trans-cyclohexane-1,2-diamine could serve as a versatile Lewis basic catalaphore and introduction of various H-bond donor entities via modification of remaining primary amine might led to discovery of new reactivities in context of bifunctional acid/base catalyst development. For this purpose, we have explored the possibility of Pd-catalyzed Buchwald-Hartwig N-arylation2 of the (1R,2R)-cyclohexane-1,2-diamine with2-haloDMAPs. Successful synthesis of 2-aminoDMAP readily in only one step encouraged us to investigate the catalytic potential of this basic catalaphore unit in pursuit of efficient bifunctional acid/base organocatalysts.3 Sulfonamides were chosen to chaperon 2-aminoDMAP base as the H-bond donor counterpart. Developed catalysts were screened in conjugate addition of acetylacetone to trans-(�)-nitrostyrene,serving testing ground for bifunctional organocatalysis. We presented 10 examples of bifunctional acid/base organocatalysts incorporating 2-aminoDMAP and systematically varied sulfonamide moieties. Additionally, thiourea and urea units were inserted as acidic catalophoric sites. The catalyst was shown to promote the conjugate addition reaction of acetylacetone and trans-(�)-nitrostyrene effectively with enantioselectivites up to 99%, whereas, urea type catalyst afforded the conjugated addition product done with diethylmalonate with enantioselectivities up to 97%.References1. a) R. P. Wurz, Chem. Rev. 2007  , 107, 5570. b) A. C. Spivey, S. Arseniyadis, Top. Curr. Chem. 2010  , 291, 233. c) C. E. M�ller, P. R. Schreiner, Angew. Chem., Int. Ed. 2011  , 50, 6012.2. a) A. S. Guram, R. A. Rennels, S. L. Buchwald, Angew. Chem. Int. Ed. 1995  , 34,1348. b) J. Louie, J. F. Hartwig, Tetrahedron Lett. 1995  , 36, 3609.3. Y. Wang, L. Deng, in Catalytic Asymmetric Synthesis, 3rd ed. (Ed.: I. Ojima), Wiley VCH: Newyork, 2010, 59-94.

2-AminoDMAP/sulfonamide and (thio)urea type organocatalysts and applications

246th National Meeting (2013)

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